[go: up one dir, main page]

EP3081673A1 - Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations - Google Patents

Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations Download PDF

Info

Publication number
EP3081673A1
EP3081673A1 EP15163811.1A EP15163811A EP3081673A1 EP 3081673 A1 EP3081673 A1 EP 3081673A1 EP 15163811 A EP15163811 A EP 15163811A EP 3081673 A1 EP3081673 A1 EP 3081673A1
Authority
EP
European Patent Office
Prior art keywords
layer
copper alloy
copper
electroplated product
product according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15163811.1A
Other languages
German (de)
English (en)
Inventor
Davide Rossi
Samuele CIAPELLI
Johanna SIEBERT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coventya SpA
Original Assignee
Coventya SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Coventya SpA filed Critical Coventya SpA
Priority to EP15163811.1A priority Critical patent/EP3081673A1/fr
Priority to PCT/EP2016/058421 priority patent/WO2016166330A1/fr
Priority to ES16716603T priority patent/ES2865279T3/es
Priority to CN201680035395.6A priority patent/CN107771228B/zh
Priority to PT167166032T priority patent/PT3283672T/pt
Priority to EP16716603.2A priority patent/EP3283672B1/fr
Publication of EP3081673A1 publication Critical patent/EP3081673A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

Definitions

  • This invention provides an electroplated product with a precious metal finishing layer that has an improved corrosion and abrasion resistance.
  • the electroplated product comprises two electroplated copper alloy layers having a different copper concentration (e.g. white bronze and yellow bronze).
  • the electroplated product is especially suitable for use in jewelry, fashion, leather, watch, eyewear, trinkets and/or lock industry.
  • Another advantage of the electroplated product is that the use of allergenic nickel or expensive palladium intermediate layers against copper migration can be dispensed with. This means that the electroplated product can be non-allergenic (nickel-free) and be provided in a more economical and environment-friendly manner.
  • a method for the production of the inventive electroplated product is presented.
  • the underlayers presently used in the fashion market to provide a high corrosion and wear resistant support for a top gold finishing layer comprises nickel and/or nickel based alloys.
  • the allergy associated with nickel and the classification of nickel salts as carcinogenic, mutagenic and reprotoxic substances makes the use of nickel and nickel based alloys more and more restricted in this market. Thus, its use has been strongly restricted, especially for fashion and jewelry applications.
  • tin alloys As an alternative to palladium, the use of different tin alloys as an intermediate barrier layer has been suggested. However, it was found that a tin content of more than 50 wt.-% in the alloy results in poor resistance to acidity and oxidants leading to corrosion and to a brightness level which are unsatisfactory for the fashion market.
  • intermediate layers consisting of chromium have been used. However, said chromium layers resulted in adhesion problems and corrosion resistance problems for the final precious metal layer such as gold.
  • the use of chromium VI is highly undesirable in the field of jewelry and fashion because it is toxic.
  • WO 2013/164165 A1 discloses a multi-layered nickel-free surface coating for sanitary application having a copper layer, a coating of at least one metal layer consisting of an alloy of copper, tin and zinc or copper and tin, a coating of at least one metal layer consisting of chromium, copper, gold, palladium or iron and a final chromium layer.
  • the intermediate layer contains a precious metal (palladium or gold) that drastically increases the cost of the electroplated product or a metal such as chromium, copper and iron that drastically reduce adherence of the final decorative layer or deteriorate corrosion resistance of the electroplated product.
  • the electroplated product is less suitable for the high requirements in the jewelry and/or fashion industry.
  • WO 2008/003216 A1 discloses an electroplated product including a copper layer on the surface of the base material, characterized in that the electroplated copper metal layer further includes a nickel substitute metal layer and the nickel substitute metal is Cu-Sn alloy, Ru, Rh, Pd, or an alloy composed of 2, 3, or 4 elements selected from Ru, Rh, Pd, and Co.
  • the use of one single layer of Cu-Sn alloy is not sufficient to target the high corrosion resistance requirement for the jewelry or fashion market and the use of precious metal intermediate layers is very expensive.
  • the prior art does not fulfill the requirements of the decorative, fashion and jewelry industry of providing in an economic and easy manner an electroplated product which is non-allergenic and has a high level of brightness and improved corrosion and abrasion resistance.
  • an electroplated product comprising
  • the electroplated product diffusion of copper from a copper containing layer into a layer containing less copper and/or a precious metal layer (like e.g. gold layer) is generally thermodynamically favoured.
  • a precious metal layer like e.g. gold layer
  • the presence of zinc in the copper containing layer was found to strongly decrease copper diffusion.
  • the first layer acts as a copper sink and prevents copper migration from copper containing layers of the electroplated product into the finishing precious metal layer of the electroplated product.
  • the electroplated product fulfills the main requirements of the fashion industry in terms of corrosion resistance, wear resistance and copper diffusion barrier properties. Compared to known alternatives in the prior art of palladium-less and nickel-less electroplated products, the inventive electroplated product shows a better corrosion performance, a better abrasion performance, an increased shelflife and a decreased production cost.
  • the copper concentration of the first copper alloy may differ from the copper concentration of the second copper alloy (in wt.-%) by an absolute value of 1 to 99 wt.-%, preferably 5 to 80 wt.-%, more preferably 10 to 60 wt.-%, even more preferably 15 to 40 wt.-%, most prefer ably 20 to 30 wt.-%.
  • the copper concentration in the second alloy can be higher than the copper concentration in the first alloy.
  • the second alloy e.g. yellow bronze
  • the first alloy having a lower copper concentration e.g. white bronze
  • the first copper alloy and/or the second copper alloy comprises Bi, Pb and/or Sb, preferably Bi. Having Bi in the alloy has the advantage that the alloy becomes both brighter and has an improved blocking ability of copper migration.
  • the first copper alloy and/or second copper alloy may also comprise phosphorus and/or silicon in the alloy.
  • the first copper alloy is white bronze and/or the second copper alloy is yellow bronze.
  • the fourth layer may be disposed on the second or third layer.
  • the electroplated product does not comprise palladium.
  • a layer comprising or consisting of a hydrophobic substance is disposed on the fourth layer, preferably a monolayer of a hydrophobic substance, more preferably a monolayer of a hydrophobic substance comprising thiol groups, especially a monolayer of alkanethiol monomers or alkanethiol polymers like e.g. octadecanethiol monomers.
  • This has the advantage that the surface of the finishing precious metal layer is made more hydrophobic and thus less prone to corrosion. Especially acid corrosion and corrosion due to sweat or interaction with leather is decreased. If the layer is only monoatomic in thickness, it is not visible and does not affect the appearance of the electroplated products.
  • the precious metal may be selected from the group consisting of gold, silver, platinum, ruthenium, rhodium, palladium, osmium, iridium and alloys thereof, preferably gold, silver, palladium and alloys thereof, more preferably gold, palladium and alloys thereof, most preferably gold.
  • the base material may comprise or consist of bronze, brass, zamak, alpaca, copper alloy, tin alloy and/or steel.
  • the base material may be an article selected from the group consisting of jewelry, fashion, leather industry, watch, eyewear, trinket and lock.
  • Example 1 Composition and properties of employed white and yellow bronze
  • the sample forms the cathode and a thin (4 mm diameter) copper tube forms the anode.
  • a small O-ring separates the anode from the cathode.
  • High-purity argon is pumped into the anode chamber.
  • a high voltage (DC or RF) between sample and anode ionizes the argon to produce a glow discharge.
  • the excited argon ions bombard the electroplated product sample and cause uniform sputtering of the sample surface. Atoms ejected are then excited by an Argon plasma, and finally come back to their fundamental energy level, emitting a characteristic X-ray photon.
  • Emitted photons whose energy is characteristic of the energy level of a chemical element, are then collected by photomultipliers.
  • the intensity of each emission depends on the concentration of the element in the sample.
  • the recorded signals are processed to obtain the distribution of the elements according to the erosion time.
  • GDOES provides depth profiling analysis of solids like metals, powders, polymers, glasses and ceramics (in the present case: depth profiling of electroplated substrates).
  • GDOES GDOES-like e.g. C, N and O.
  • the concentration of each chemical element Au, Cu, Zn, Sn and eventually Ni (when this element is present to determine the Pd-Ni coating) is shown (y-axis in wt.-%) as a function of the distance from the surface of the finishing layer towards the base material of the electroplated product (x-axis in ⁇ m).
  • the thicknesses of the layers given for the process of the argon ablation (abscissa) and the metal concentrations (ordinate) are not normalized, but reflect the progress of the metal migration from the as-plated to the annealed state (annealing at 180 °C for 24 h).
  • An electroplated nickel-containing product of the prior art comprises the following layers electrolytically deposited on a brass substrate: bright nickel layer: 10 ⁇ m nickel phosphorus layer: 2 ⁇ m gold layer as finishing layer: 0.5 ⁇ m
  • Said electroplated nickel-containing product has the following properties: NFS 80772: 24 HOURS; ABRASION WITH TURBULA: 5 MINUTES LEATHER INTERACTION UNDER ISO 4611: 96 HOURS; ISO 4538: 48 HOURS; ISO 4524/2: 8 HOURS; ISO 4611: 96 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 30 min.
  • Turbula test is to simulate general wear that results from wearing the parts.
  • the test was performed using an industrial rotating machine (Turbula, model T2F, Willy A. Bachofen AG Maschinenfabrik, Switzerland).
  • Abrasive load was composed of abrasion ceramic elements mixed with fresh water containing a surface tension agent. Detailed information on the size of the ceramic elements is described in the ISO 23160 reference (see Table 1 - page 3). Test duration was 30 minutes. Evaluation of wear was done by visual inspection and comparison with reference samples. In particular, a color change after abrasion was used to evaluate wear resistance of the tested parts. The Turbula test is considered positive if no colour change is visible in the tested parts, especially on the edges or regions that are more exposed.
  • An electroplated nickel-less product of the prior art comprises the following layers electrolytically deposited on a brass substrate: bright copper layer: 10 ⁇ m white bronze layer: 2 ⁇ m gold layer as finishing layer: 0.5 ⁇ m
  • Said electroplated nickel-free product has the following properties: NFS 80772: 12 HOURS; ABRASION WITH TURBULA: 5 MINUTES LEATHER INTERACTION UNDER ISO 4611: 48-72 HOURS; ISO 4538: 48 HOURS; ISO 4524/2: 8 HOURS; ISO 4611: 96 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 30 min.
  • the reason for which the bronze layer is very thin is related with the level of quality of bronze plating processes known in the prior art that do not allow exceeding 2 ⁇ m of the deposit while maintaining the desired bright aspect. In other words, this is the reason why thicker deposits of white bronze are undesirable for the jewelry and/or fashion industry because of a lack of brightness.
  • the precious metal layers are regularly a very thin deposit (approx. 0.5 ⁇ m), it is easy for corrosive media or mechanical action to reach the underlying bronze layer.
  • Said bronze layer is softer than nickel and has a slightly lower thickness. Thus, it is less resistant to mechanical stress and can be damaged easily.
  • the underlying copper layer Upon damage of the white bronze layer, the underlying copper layer will appear and be exposed to the atmosphere and oxidation. For these reasons, the nickel-free plated parts are easier oxidized by aggressive media, like leather and the acid sweat of human skin.
  • An electroplated nickel-containing product of the prior art comprises the following layers electrolytically deposited on a brass substrate: bright copper layer: 10 ⁇ m white bronze layer: 2 ⁇ m palladium-nickel layer: 0.3 ⁇ m gold layer as finishing layer: 0.5 ⁇ m
  • Said electroplated nickel-free product has the following properties: NFS 80772: 24 HOURS; ABRASION WITH TURBULA: 5 MINUTES LEATHER INTERACTION UNDER ISO 4611: 48-72 HOURS; ISO 4538: 48 HOURS; ISO 4524/2: 8 HOURS; ISO 4611: 96 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 30 min.
  • a first example of an inventive electroplated nickel-less product comprises the following layers electrolytically deposited on a brass or zamak substrate: bright copper layer: 10 ⁇ m white bronze layer: 2-4 ⁇ m yellow bronze layer: 3-4 ⁇ m gold layer as finishing layer: 0.5 ⁇ m
  • a second example of an inventive electroplated nickel-less product comprises the following layers electrolytically deposited on a brass or zamak substrate: bright copper layer: 10 ⁇ m yellow bronze layer: 3-4 ⁇ m white bronze layer: 2-3 ⁇ m palladium layer as finishing layer: 0.5 ⁇ m
  • the electroplated nickel-free product of the first example and of the second example has the following properties: NFS 80772: 24 HOURS; ABRASION WITH TURBULA: 5 MINUTES LEATHER INTERACTION UNDER ISO 4611: 96 HOURS; ISO 4538: 48 HOURS; ISO 4524/2: 8 HOURS; ISO 4611: 96 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 30 min.
  • the improvement of performance is essentially related to the protection of the copper underlayer on the one hand and to the conservation of the quality of the top gold layer on the other hand by the presence of both the white and yellow bronze layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
EP15163811.1A 2015-04-16 2015-04-16 Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations Withdrawn EP3081673A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP15163811.1A EP3081673A1 (fr) 2015-04-16 2015-04-16 Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations
PCT/EP2016/058421 WO2016166330A1 (fr) 2015-04-16 2016-04-15 Produit à revêtement électrolytique ayant une couche de finition de métal précieux et une meilleure résistance à la corrosion, son procédé de production et ses utilisations
ES16716603T ES2865279T3 (es) 2015-04-16 2016-04-15 Producto electrodepositado con una capa de acabado de metal precioso y resistencia a la corrosión mejorada, método para su producción y usos del mismo
CN201680035395.6A CN107771228B (zh) 2015-04-16 2016-04-15 具有贵金属精整层和改善的耐腐蚀性的电镀产品及其制造方法和用途
PT167166032T PT3283672T (pt) 2015-04-16 2016-04-15 Produto galvânico possuindo uma camada de acabamento de metal precioso e resistência a corrosão melhorada, método para a sua produção e suas utilizações
EP16716603.2A EP3283672B1 (fr) 2015-04-16 2016-04-15 Produit à revêtement électrolytique ayant une couche de finition de métal précieux et une meilleure résistance à la corrosion, son procédé de production et ses utilisations

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP15163811.1A EP3081673A1 (fr) 2015-04-16 2015-04-16 Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations

Publications (1)

Publication Number Publication Date
EP3081673A1 true EP3081673A1 (fr) 2016-10-19

Family

ID=52946395

Family Applications (2)

Application Number Title Priority Date Filing Date
EP15163811.1A Withdrawn EP3081673A1 (fr) 2015-04-16 2015-04-16 Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations
EP16716603.2A Active EP3283672B1 (fr) 2015-04-16 2016-04-15 Produit à revêtement électrolytique ayant une couche de finition de métal précieux et une meilleure résistance à la corrosion, son procédé de production et ses utilisations

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP16716603.2A Active EP3283672B1 (fr) 2015-04-16 2016-04-15 Produit à revêtement électrolytique ayant une couche de finition de métal précieux et une meilleure résistance à la corrosion, son procédé de production et ses utilisations

Country Status (5)

Country Link
EP (2) EP3081673A1 (fr)
CN (1) CN107771228B (fr)
ES (1) ES2865279T3 (fr)
PT (1) PT3283672T (fr)
WO (1) WO2016166330A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3733930A1 (fr) * 2019-05-03 2020-11-04 IWG Ing. W. Garhöfer Gesellschaft m. b. H. Système de revêtement destiné à l'application par dépôt galvanique sur un lingot
IT202000011203A1 (it) * 2020-05-15 2021-11-15 Bluclad S P A Lega di bronzo inossidabile e suo impiego in prodotti galvanizzati
DE102021117095A1 (de) 2021-07-02 2023-01-05 Umicore Galvanotechnik Gmbh Bronzeschichten als Edelmetallersatz

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3540097A1 (fr) 2018-03-13 2019-09-18 COVENTYA S.p.A. Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
CN118308768A (zh) * 2024-04-10 2024-07-09 深圳市宸象大数据有限公司 一种贵金属软链的制备方法及贵金属软链

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999048682A1 (fr) * 1998-03-27 1999-09-30 University Of Pittsburgh Article, preparation resistant au ternissement, procede de fabrication et procedes d'utilisation associes
JP2003096592A (ja) * 2001-09-20 2003-04-03 Kawaguchiko Seimitsu Co Ltd 時計用外装部品
WO2008003216A1 (fr) 2006-06-26 2008-01-10 Byd Company Limited Produit à revêtement électrolytique et procédé de préparation de celui-ci
EP2565297A2 (fr) * 2011-08-30 2013-03-06 Rohm and Haas Electronic Materials LLC Promotion de l'adhérence de bronze blanc exempt de cyanure
WO2013164165A1 (fr) 2012-05-02 2013-11-07 Umicore Galvanotechnik Gmbh Revêtement de surface multicouche comprenant une couche de recouvrement en chrome sans couche en nickel
WO2015039152A1 (fr) * 2013-09-18 2015-03-26 Ing.W.Garhöfer Gesellschaft M.B.H. Dépôt de couches de cu, sn, zn sur des substrats métalliques

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2779156B1 (fr) * 1998-05-29 2000-08-18 Sarthoise De Revetements Elect Depot d'alliages jaune clair
KR100494820B1 (ko) * 2000-06-27 2005-06-14 시티즌 도케이 가부시키가이샤 백색 피막을 갖는 장식품 및 그 제조 방법
CN101195924A (zh) * 2006-12-05 2008-06-11 比亚迪股份有限公司 一种电镀产品及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999048682A1 (fr) * 1998-03-27 1999-09-30 University Of Pittsburgh Article, preparation resistant au ternissement, procede de fabrication et procedes d'utilisation associes
JP2003096592A (ja) * 2001-09-20 2003-04-03 Kawaguchiko Seimitsu Co Ltd 時計用外装部品
WO2008003216A1 (fr) 2006-06-26 2008-01-10 Byd Company Limited Produit à revêtement électrolytique et procédé de préparation de celui-ci
EP2565297A2 (fr) * 2011-08-30 2013-03-06 Rohm and Haas Electronic Materials LLC Promotion de l'adhérence de bronze blanc exempt de cyanure
WO2013164165A1 (fr) 2012-05-02 2013-11-07 Umicore Galvanotechnik Gmbh Revêtement de surface multicouche comprenant une couche de recouvrement en chrome sans couche en nickel
WO2015039152A1 (fr) * 2013-09-18 2015-03-26 Ing.W.Garhöfer Gesellschaft M.B.H. Dépôt de couches de cu, sn, zn sur des substrats métalliques

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3733930A1 (fr) * 2019-05-03 2020-11-04 IWG Ing. W. Garhöfer Gesellschaft m. b. H. Système de revêtement destiné à l'application par dépôt galvanique sur un lingot
IT202000011203A1 (it) * 2020-05-15 2021-11-15 Bluclad S P A Lega di bronzo inossidabile e suo impiego in prodotti galvanizzati
WO2021229481A1 (fr) * 2020-05-15 2021-11-18 Bluclad S.R.L. Alliage de bronze inoxydable et son utilisation dans des produits galvanisés
DE102021117095A1 (de) 2021-07-02 2023-01-05 Umicore Galvanotechnik Gmbh Bronzeschichten als Edelmetallersatz
US12195869B2 (en) 2021-07-02 2025-01-14 Umicore Galvanotechnik Gmbh Bronze layers as noble metal substitutes

Also Published As

Publication number Publication date
EP3283672B1 (fr) 2021-03-17
WO2016166330A1 (fr) 2016-10-20
EP3283672A1 (fr) 2018-02-21
ES2865279T3 (es) 2021-10-15
PT3283672T (pt) 2021-04-28
CN107771228A (zh) 2018-03-06
CN107771228B (zh) 2020-05-05

Similar Documents

Publication Publication Date Title
EP3283672B1 (fr) Produit à revêtement électrolytique ayant une couche de finition de métal précieux et une meilleure résistance à la corrosion, son procédé de production et ses utilisations
EP2829633B1 (fr) Élément décoratif rigide
EP3312309B1 (fr) Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations
EP2135972A1 (fr) Revêtement d'alliage d'or, stratifié de gaine de revêtement d'alliage d'or et élément de gaine de revêtement d'alliage d'or.
EP0808921B1 (fr) Element ornemental
US11408066B2 (en) Decorative member and method for producing the same
EP3356579B1 (fr) Bain d'électrodéposition pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cet alliage, substrat comprenant ledit alliage et utilisations de ce substrat
EP3765658B1 (fr) Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
US11760887B2 (en) Titanium material
KR101803219B1 (ko) 용기용 강판 및 그 제조 방법
EP2864526A1 (fr) Processus pour la production d'un composant de vannes, de raccords ou d'ensembles robinets et composant
CN104789963B (zh) 一种金银首饰包装用复合镀层捆带的生产方法
KR20230050238A (ko) PtRu 합금 도금액 및 PtRu 합금막의 도금 방법
EP3445582A1 (fr) Alliage de phosphore-cobalt-nickel et son utilisation dans des procédés de placage d'objets en métal non précieux avec des métaux précieux
EP4001472A1 (fr) Procédé de préparation d'un produit électroplaqué par dépôt d'une sous-couche, d'une couche barrière de diffusion et d'une couche supérieure sur la surface d'un substrat et produit électroplaqué ainsi préparé
CA2858875A1 (fr) Flan monetaire
EP4043202A1 (fr) Alliage pt-ni non allergénique électroplaqué et bain et cycle galvanique associés
WO2021229481A1 (fr) Alliage de bronze inoxydable et son utilisation dans des produits galvanisés
TW202014535A (zh) 硬質裝飾構件及其製造方法
JP2000141999A (ja) 装飾部材及びその製造方法
HK1003179B (en) Ornamental member
HK1132767A (en) Gold alloy coating, gold alloy coating clad laminate and gold alloy coating clad member

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20170420